Laser annealing method and laser annealing device

ABSTRACT

A laser-annealing method includes the steps of a first step of cleaning a non-monocrystal silicon film formed on a substrate, and a second step of laser-annealing the non-monocrystal silicon film in an atmosphere containing oxygen therein, wherein the first and second steps are conducted continuously without being exposed to the air. Also, a laser-annealing device includes a cleaning chamber, and a laser irradiation chamber, wherein a substrate to be processed is transported between the cleaning chamber and the laser irradiation chamber without being exposed to the air.

This is a continuation of U.S. application Ser. No. 09/390,513, filedSep. 3, 1999, now U.S. Pat. No. 6,348,369, which is a continuation ofU.S. application Ser. No. 08/735,554, filed Oct. 23, 1996 (U.S. Pat. No.6,027,960).

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method of laser-annealing anamorphous silicon film or a crystalline silicon film formed on aninsulating substrate made of glass or the like to crystallize the filmor to improve the crystallinity.

2. Description of the Related Art

In recent years, a technique has been widely researched in whichlaser-annealing is conducted on an amorphous silicon film or acrystalline silicon film (a silicon film having crystallinity such aspolycrystal or microcrystal, which is not mono-crystal) formed on aninsulating substrate made of glass or the like, that is, anon-monocrystal silicon film, to crystallize those films or to improvethe crystallinity.

The crystalline silicon film formed by laser-annealing, for its highmobility, has been widely employed for a monolithic type liquid-crystalelectro-optic device, etc., in which a thin-film transistor (TFT) isformed using the crystalline silicon film, and TFTs for pixel drivingand drive circuits are then fabricated, for example, on a single glasssubstrate.

Also, a method has been preferred to employ in which pulsed laser beamssuch as an excimer laser is processed by an optical system so as to beformed into beams having a square spot of several cm² in cross sectionor beams having a linear shape of several mm width x several tens cm,and laser-annealing is conducted by scanning the laser beam thusprocessed (while the radiation position of the laser beams is movedrelatively with respect to a surface to be irradiated), because it isimproved in productivity and excellent industrially.

In particular, the use of the linear laser beam makes the productivityhigh because laser beams can be irradiated on the overall surface to beirradiated by the scanning operation conducted only in a directionperpendicular to the linear direction, which is different from a case inwhich spot-like laser beams that require the right and left scanningoperation as well as the forward and backward scanning operation areused.

There arise several problems in conducting laser-annealing on thenon-monocrystal silicon film by scanning spot-like or linear laser beamsemitted from a pulsed laser beam source thereon.

For example, in the case where laser-annealing is conducted in the air,there arises such a problem that impurities of carbon contained in theair and other materials are liable to be mixedly inserted into the film,to thereby deteriorate the various characteristics such as the quality,the crystallinity or the mobility of the crystalline silicon film whichhas been annealed.

Also, in the case where laser-annealing is conducted by scanning beamswhich are spot-shaped or linear on the surface to be irradiated in avacuum atmosphere or inactive gas atmosphere such as nitrogen, thefollowing problems are caused in comparison with annealing in the air.

1) The crystallinity is deteriorated. That is, a high crystallinitycannot be obtained without largely increasing the energy density of alaser beam in comparison with annealing in the air.

2) The uniformity in the film of the crystal is deteriorated. Locationswhere the crystallinity is high and locations where the crystallinity islow are distributed in the film. For example, in the case where linearlaser beams are scanned in a direction perpendicular to the lineardirection of the beam, locations where the crystallinity is high andlocations where the crystallinity is low appear in the form of a stripepattern on the film surface. Accordingly, in the case where a pluralityof thin-film transistors are manufactured using the fabricatedcrystalline silicon film, a variety of characteristics such as athreshold value or mobility are different depending on a position of thethin-film transistor on a substrate.

3) The use efficiency of an energy is deteriorated. For the purpose ofenhancing the crystallinity, the energy density of laser must beincreased. As the energy density is increased, the power consumption isalso increased. In addition, the entire laser irradiating deviceincluding a laser oscillator and a circuit, a gas and an optical systemsis largely consumed, resulting in the increased costs of a manufactureddevice. Also, although the crystallinity is increased as the energydensity of laser is increased, an entire film which has been subjectedto laser-annealing is remarkably roughened, thereby making it hard tomanufacture the device by processing the film.

SUMMARY OF THE INVENTION

The present invention has been made to solve the above problems of theconventional device, and therefore an object of the present invention isto provide a laser-annealing method which is capable of remarkablyimproving crystallinity and uniformity, as well as the use efficiency ofenergy.

In order to solve the above problems, according to one aspect of thepresent invention, there is provided a laser-annealing method whichcomprises the steps of: a first step of cleaning a non-monocrystalsilicon film formed on a substrate; and a second step of laser-annealingsaid non-monocrystal silicon film in an atmosphere containing oxygentherein; wherein said first and second steps are conducted continuouslywithout being exposed to the air.

In the above method, it is preferable that said second step is conductedafter an upper surface of said non-monocrystal silicon film has beenoxidized in the atmosphere containing oxygen therein.

According to another aspect of the present invention, there is provideda laser-annealing method which comprises the steps of: a first step ofcleaning a non-monocrystal silicon film formed on a substrate; a secondstep of oxidizing an upper surface of said non-monocrystal silicon filmto form a silicon oxide film; and a third step of laser-annealing saidnon-monocrystal silicon film; wherein at least said first and secondsteps of the respective steps are conducted continuously without beingexposed to the air.

In the above method, it is preferable that said third step is conductedin a nitrogen atmosphere.

According to still another aspect of the present invention, there isprovided a laser-annealing device which comprises at least a cleaningchamber and a laser irradiation chamber, in which a substrate to beprocessed is transported between said cleaning chamber and said laserirradiation chamber without being exposed to the air.

According to yet still another aspect of the present invention, there isprovided a laser-annealing device which comprises at least a cleaningchamber, a preliminary heating chamber and a laser irradiation chamber,in which a substrate to be processed is transported between saidcleaning chamber and said preliminary heating chamber without beingexposed to the air.

In this specification, the above term “continuously” means that no stepin which impurities or other undesired materials are stuck on thenon-monocrystal silicon film exists between said first and second steps.

Accordingly, for example, to provide a substrate transporting step, analignment step, an annealing step, a step of heating the substrate up toa temperature necessary for the second step, a step of dehydrogenationstep by heating, and so on fall within the “continuation” in thisspecification.

On the other hand, in the case where a step of exposing anon-monocrystal silicon film to a specific atmosphere that changes thequality of the film, a ion doping step, a film forming step, an etchingstep, a plasma processing step, a film coating step, and so on areconducted between the above first and second steps, these steps do notfall the definition of the “continuation” in this specification.

According to the present invention, in laser-annealing thenon-monocrystal silicon film to crystallize the film or improve thecrystallinity, the upper surface of the non-monocrystal silicon film isoxidized in an atmosphere containing oxygen therein, to particularlyform a silicon oxide film 100 Å or less in thickness, and thereafter alaser beam is irradiated onto the silicon oxide film.

Also, according to the present invention, a laser beam is irradiatedonto the non-monocrystal silicon film in a state where it is disposed inan atmosphere containing oxygen therein.

Further, according to the present invention, a step of cleaning thenon-monocrystal silicon film to remove a natural oxide film orimpurities, and a step of irradiating a laser beam onto thenon-monocrystal silicon film in an atmosphere containing oxygen thereinor a step of forming a silicon oxide film on the upper surface of thenon-monocrystal silicon film in an atmosphere containing oxygen thereinare continuously conducted without being exposed to the air.

When the upper surface of the non-monocrystal silicon film is oxidizedto form the silicon oxide film 100 Å or less in thickness, and thesilicon oxide film is laser-annealed in this state, not only thecrystalline silicon film purer than that formed by laser-annealing inthe air is obtained, but also the following excellent characteristicsare obtained in comparison with a case of conducting laser annealing inthe air or in another atmosphere.

1) The crystallinity of the crystalline silicon film is improved.

2) The crystallinity of the crystalline silicon film is uniformed in thefilm surface.

3) The energy density of laser necessary for crystallization is lowered.

With the formation of the very-thin oxide silicon film, it is presumedthat the reflection/discharge of energy of a laser beam irradiated ontothe non-monocrystal silicon film is suppressed so that a given energy iskept within the film. Therefore, a large amount of energy can be givento the non-monocrystal silicon film more than a case where no siliconoxide film is provided, to thereby improve the crystallinity.

Simultaneously, because the nonuniformity and dispersion of the energydensity for each pulse of a laser beam are prevented, the crystallinityis also uniformed in quality within the film surface.

Further, because the reflection/discharge of a laser energy to anatmosphere is reduced so that the energy is effectively used forcrystallization, the energy density of an irradiated laser beam can belowered.

When a laser beam is irradiated to a non-monocrystal silicon film in astate where silicon oxide film is formed on the non-monocrystal siliconfilm at a high energy density as in the state where no silicon oxidefilm is provided, an excessive energy is given though an energy loss isreduced, with the result that the entire film is remarkably roughenedalthough the crystallinity is enhanced. It is very hard to manufacture adevice such as a thin-film transistor using such a film.

Also, it is preferable that the upper surface of the non-monocrystalsilicon film is cleaned by HF aqueous solution or aqueous solutioncontaining HF and H₂O₂ therein to remove the natural oxide film beforeconducting laser-annealing. It is preferable that the subsequent step ofmanufacturing the silicon oxide film, or step of laser-annealing in anatmosphere containing oxygen therein is conducted while heating thesubstrate because the rate of forming the silicon oxide film isimproved. The above steps may be conducted while irradiating ultravioletrays on the film.

In particular, it is preferable that the above cleaning step and thesubsequent laser annealing step conducted in an oxygen atmosphere arecontinuously conducted without being exposed to the air, or the cleaningstep, a heating (silicon oxide film forming) step which is conducted inan oxygen atmosphere, and the laser-annealing step are continuouslyconducted without being exposed to the air.

With the above method, the silicon oxide film is formed from the veryclean upper surface of the non-monocrystal silicon film. As a result,the silicon oxide film formed becomes more uniform in thickness andquality, to thereby improve the uniformity of the quality of the filmcrystallized by laser-annealing within the substrate surface.

Further, the invasion by impurities into the non-monocrystal siliconfilm during laser-annealing is more reduced. As a result, a variety ofcharacteristics such as the mobility or the threshold value of thedevice such as a thin-film transistor which is manufactured using theabove film can be more stabilized within the substrate surface as wellas between lots.

The atmosphere containing oxygen is preferably comprised of only oxygen,or the mixture gas of oxygen and an inactive gas such as nitrogen,helium or argon. The mixture gas preferably contains oxygen of 1% ormore, more preferably 5% or more under the atmospheric pressure. Whenthe oxygen content is 1% or less, a period of time necessary for forminga sufficient silicon oxide film becomes extremely long, or the siliconoxide film cannot be formed, thus obtaining the insufficient effect ofthe present invention. Therefore, it is not for practical use. If theoxygen content is 5% or more, the effect of the present invention isstably obtained.

In the case where air is used as an atmosphere containing oxygen informing the silicon oxide film, the impurities such as carbon in the airis mixed into the film to be annealed, often resulting in cases in whichthe mobility of the crystalline silicon film and other variouscharacteristics are lowered, or the characteristics for each lot areunstabilized. It should be noted that it is effective that, after thesilicon oxide film is manufactured in another atmosphere, the film islaser-annealed in the air atmosphere.

Also, it is particularly preferable that oxygen or inactive gas whichconstitutes an atmosphere containing oxygen is 99.9% (3N) or higher but99.99999% (7N) or lower in purity. With an atmosphere using the gas ofthis purity, carbon, water, hydrocarbon and other impurities areprevented from being mixed into the crystalline silicon film, to therebyobtain the crystalline silicon film which is stabilized in quality andcharacteristics and is excellent in characteristic. When the purity ofoxygen or inactive gas which forms an atmosphere is less than 3N, thereis little difference from a case of using the air atmosphere, and thefilm characteristic is liable to be unstabilized by the impurities.Also, even though the gas having a high purity more than 7N is used,there is no large difference from a case where the purity is 7N or less,but the costs are increased. Therefore, it is not preferable.

Moreover, when the thickness of the above silicon oxide film is set to100 Å or more, the amount of mixture of the silicon oxide film into thecrystalline silicon film is increased by the irradiation of a laserbeam, to thereby lower a variety of characteristics such as thecrystallinity or the mobility of the crystalline silicon film. On theother hand, when the thickness of the silicon oxide film is too narrowedto about 5 Å or less, the above-mentioned effects of the presentinvention is remarkably deteriorated. The thickness of the silicon oxidefilm is suitably set to 5 to 100 Å, preferably 10 to 50 Å, and morepreferably 20 to 40 Å.

The pressure applied when conducting laser-annealing may be atmosphericpressure. In the case where the pressure applied when conductinglaser-annealing is reduced to atmospheric pressure or less, inparticular, to 0.01 to 700 Torr, the upper surface or the entirety ofthe crystalline silicon film is less roughened by the irradiation ofpulsed laser beams by plural times, which is preferable. In other words,the pulsed laser beam irradiation resistance of the crystalline siliconfilm is improved so that a film less roughened is obtained. In the casewhere the pressure applied when conducting laser-annealing is more than700 Torr, the roughness of the film is nearly identical with that in thecase of atmospheric pressure. In the case where the pressure is lessthan 0.01 Torr, such effects as improvements in crystallinity,uniformity in quality, and the energy efficiency are then remarkablydeteriorated.

It is preferable that the irradiation of a laser beam is conducted byscanning a laser beam which is slot-shaped or linear in cross section ona surface to be irradiated.

Also, it is preferable that the laser beam is irradiated from a pulsedlaser source.

To implement the present invention, the non-monocrystal silicon film isexposed to an atmosphere containing oxygen therein, or the upper surfaceof the non-monocrystal silicon film is oxidized by heating or theirradiation of ultraviolet rays under the condition where thenon-monocrystal silicon film is exposed to an atmosphere containingoxygen therein, and then the film thus obtained is laser-annealed.

After the upper surface of the non-monocrystal silicon film has beenoxidized in the atmosphere containing oxygen in one chamber, the filmmay be laser-annealed in the atmosphere containing oxygen or in anotheratmosphere in another chamber.

Also, in the case where laser-annealing is conducted in an atmospherecontaining oxygen therein within an atmosphere-controllable vessel,oxidation and laser-annealing can be conducted within one vessel, thusreducing the manufacture processes. In this case, it is preferable thata substrate is heated when conducting laser-annealing.

The silicon oxide film according to the present invention is completelydifferent from a cap layer (what prevents the roughness (ridges) on thesurface of the silicon film which is caused during laser-annealing bythe mechanical strength of a film which is formed as a silicon oxidefilm or a silicon nitride film several 1000 Å in thickness on theamorphous silicon film when conducting laser-annealing mainly using asmall-output continuous oscillation laser).

The above thick silicon oxide film, when using a large-output pulselaser such as an excimer layer as in the present invention, allows alarge amount of silicon oxide to be mixed into a silicon film whenconducting laser-annealing as described above, resulting in thedeterioration of the quality and the characteristics of the crystallinesilicon film formed.

When laser-annealing is conducted in the state where the cap layer isprovided, the film is crystallized in the state where it is pressedagainst the cap layer. As a result, the growth of crystal is suppressedto deteriorate the crystallinity of the crystalline silicon film formed.In addition, a large stress remains inside the crystalline silicon film.

In the present invention, because the silicon oxide film is extremelythin, the growth of crystal is hardly suppressed, with the results thata higher crystallinity is obtained than that of the cap layer, and aninternal stress can be also considerably reduced.

Hence, a thickness of the film that produces a mechanical strength tothe extent that the ridges can be suppressed is improper for the siliconoxide film according to the present invention. Because the silicon oxidefilm according to the present invention is extremely thin to 100 Å orless, most of the silicon oxide film is scattered by the plural times ofirradiation of pulsed laser beams so as to be removed.

The above and other objects and features of the present invention willbe more apparent from the following description taken in conjunctionwith the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing a laser irradiation chamber in accordancewith an embodiment of the present invention;

FIGS. 2A to 2F are diagrams showing a manufacturing process inaccordance with the embodiment of the present invention;

FIG. 3 is an upper view showing a laser annealing unit in accordancewith the embodiment of the present invention;

FIG. 4 is a graph showing a relation between the energy density of alaser beam and the Raman half-value and half-width of the crystallinesilicon film which has been laser-annealed in the case wherelaser-annealing is conducted in a variety of atmospheres;

FIG. 5 is an upper view showing a laser annealing unit in accordancewith the embodiment of the present invention; and

FIG. 6 is an upper view showing a continuous processing unit inaccordance with the embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Now, a description will be given in more detail of embodiments of thepresent invention with reference to the accompanying drawings.

First Embodiment

A first embodiment shows an example in which laser-annealing isconducted on a non-monocrystal silicon film in an atmosphere containingoxygen therein.

FIG. 2 shows a manufacturing process in accordance with this embodiment.First, a silicon oxide film 202 which is 2000 Å in thickness is formedas an under layer on a substrate 201 which is made of Corning 1737having 127 mm² in area, and a non-monocrystal silicon film which is 500Å in thickness is formed on the silicon oxide film 202, which process iscontinuously conducted through the plasma CVD technique.

Subsequently, a nickel acetate aqueous solution of 10 ppm is coated onthe amorphous silicon film through the spin coating technique to form anickel acetate layer. A surface active agent is preferably added to thenickel acetate aqueous solution. Although the nickel acetate layer isnot limited to a film shape since it is extremely thin, it does notcause any problems in the subsequent processes.

Then, thermal annealing is conducted on the substrate 201 on which therespective films are laminated in the above manner, at 600° C. for fourhours so that the amorphous silicon film is crystallized, to therebyform a crystalline silicon film 203 (FIG. 2A).

In this situation, nickel which is a catalytic element serves as anucleus for crystal growth to facilitate crystallization. The action ofnickel enables crystallization of the amorphous silicon film at a lowtemperature for a short period of time, that is, at 600° C. for fourhours. The details are disclosed in Japanese Patent UnexaminedPublication No. Hei 6-244104.

The density of the catalytic element is preferably set to 1×10¹⁵ to 10¹⁹atoms/cm³. In the case of a high density such as 1×10¹⁹ atoms/cm³ ormore, the crystalline silicon film exhibits the metallic property sothat the semiconductor characteristics disappear. In this embodiment,the density of the catalytic element in the crystalline silicon film isset to 1×10¹⁷ to 5×10¹⁸ atoms/cm³ at the minimum in the film. Thosevalues are values which have been analyzed and measured through thesecondary ion mass spectrometer (SIMS).

In order to further enhance the crystallinity of the crystalline siliconfilm 203 thus obtained, laser-annealing is conducted using an excimerlaser.

A laser irradiation chamber in accordance with this embodiment is shownin FIG. 1 that shows a side cross-sectional view of the laserirradiation chamber.

FIG. 3 shows an upper view of a laser annealing unit in accordance withthis embodiment. In this example, a multi-chamber type laser annealingunit shown in FIG. 3 is employed. A cross-sectional view taken along aline A–A′ in FIG. 3 corresponds to FIG. 1.

In FIG. 1, a laser irradiation chamber 101 functions so that a pulsedlaser beam, which is irradiated from a laser oscillation unit 102 andthen processed into a linear shape in cross section by an optical system112, is reflected by a mirror 103, and then irradiated on a substrate105 to be processed through a window 104 which is made of quartz.

The laser oscillation unit 102 as used in this embodiment is the onethat oscillates XeCl excimer laser beams (wavelength of 308 nm) Instead,a KrF excimer laser (wavelength of 248 nm) may be used.

The substrate 105 to be processed is located on a stage 111 disposed ona table 106 and is kept at a predetermined temperature (100 to 700° C.)by a heater disposed within the table 106.

The table 106 is moved in a direction perpendicular to a lineardirection of a linear laser beam in such a manner that the laser beamcan be irradiated on the upper surface of the substrate 105 to beprocessed in the scanning manner.

The laser irradiation chamber 101 which can control atmosphere includestherein a vacuum gas-exhaust pump 108 as pressure-reduction andgas-exhaust means. Also, the laser irradiation chamber 101 alsoincludes, as gas supply means, a gas supply pipe 109 connected to ahydrogen bomb through a valve and a gas supply pipe 110 connected to anitrogen or another-gas bomb through a valve.

The laser irradiation chamber 101 is coupled to a substrate transferchamber 302 through a gate valve 301.

In FIG. 3, the laser irradiation chamber 101 shown in FIG. 1 is coupledto the substrate transfer chamber 302 through the gate valve 301.

The unit shown in FIG. 3 will be described. Within a load/unload chamber306 is disposed a cassette 312 that receives therein a large number ofsubstrates 105 to be processed, for example, 20 substrates 105. A singlesubstrate 105 is moved from the cassette 312 to an alignment chamber 303by a robot arm 305.

In the alignment chamber 303 is disposed an alignment mechanism forcorrecting the positional relation between the substrate 105 to beprocessed and the robot arm 305. The alignment chamber 303 is connectedto the load/unload chamber 306 through a gate valve 307.

A preliminary heating chamber 308 is so designed as to preliminarilyheat a substrate 105 to be laser-annealed up to a predeterminedtemperature to reduce a period of time necessary for heating thesubstrate 105 in the laser irradiation chamber 101, resulting in animprovement of throughput.

The preliminary heating chamber 308 has its interior formed ofcylindrical quartz. The cylindrical quartz is surrounded by a heater.The preliminary heating chamber 308 also includes a substrate holderwhich is made of quartz. The substrate holder is provided with asusceptor that can receive a large number of substrates 105 therein. Thesubstrate holder moves up and down by an elevator. The substrate 105 isheated by the heater. The preliminary heating chamber 308 is coupled tothe substrate transfer chamber 302 by the gate valve 309.

The substrate 105 which has been preheated for a predetermined period oftime in the preliminary heating chamber 308 is brought back to thesubstrate transfer chamber 302 by the robot arm 305. Then, after thesubstrate 105 is aligned again in the alignment chamber 303, it is movedto the laser irradiation chamber 101 by the robot arm 305.

After the completion of irradiation of the laser beam, the substrate 105to be processed is taken out to the substrate transfer chamber 302 bythe robot arm 305 before being moved to an annealing chamber 310.

The cooling chamber 310 is connected to the substrate transfer chamber302 through a gate valve 311, and the substrate 105 to be processedwhich is disposed on the stage made of quartz is exposed to infraredrays emitted from a lamp and a reflection plate in such a manner that itis gradually cooled.

The substrate 105 to be processed which has been cooled in the coolingchamber 310 is moved to the load/unload chamber 306 by the robot arm 305and then received in the cassette 312.

In the above manner, the laser-annealing process is completed. Theabove-mentioned process is repeated, thereby being capable ofcontinuously processing a large number of substrates 105 one by one.

A process of conducting laser-annealing will be described using the unitshown in FIGS. 1 and 3. First, the substrate 105 to be processed (asubstrate 201 having a crystalline silicon film 203), after having beencleaned by an HF aqueous solution or a mixture aqueous solution of HFand H₂O₂ until a natural oxide film has been removed from the substrate105, is received in the cassette 312, and the cassette 312 is thendisposed in the load/unload chamber 306.

In FIG. 3, the substrate 105 to be processed which is transferred fromthe load/unload chamber 306 in this embodiment is transferred directlyto the laser irradiation chamber 101 without being transferred to thepreliminary heating chamber 308 after it has been subjected toalignment, in order that the substrate 105 is prevented from beingoxidized by air in the preliminary heating chamber. It should be notedthat it is effective that the substrate 105 is heated in the preliminaryheating chamber 308 to such an extent that the upper surface of thecrystalline silicon film 203 is not oxidized.

Oxygen is supplied from the gas supply pipe 109, and nitrogen issupplied from the gas supply pipe 110, respectively, to the laserirradiation chamber 101, to provide an atmosphere of oxygen 20% andnitrogen 80% therein, after vacuum has been produced in the laserirradiation chamber 101 by the vacuum air-exhaust pump 108. In thisexample, both of oxygen and nitrogen supplied into the laser irradiationchamber are 99.99999% (7N) in purity. In this situation, pressure is setto the atmospheric pressure.

The substrate 105 to be processed which has been transferred to thelaser irradiation chamber 101 is heated for about 5 minutes in the statewhere the substrate 105 is located on the stage 111 so that thetemperature of the substrate 105 reaches a temperature suitable forlaser-annealing, in this example, 200° C. The upper surface of thecrystalline silicon film 203 is oxidized by oxygen contained in anatmosphere during heating, to thereby form a pure silicon oxide film 204without being mixed with impurities such as carbon in the air. Thethickness of the crystalline silicon oxide film 204 is set to 10 to 50Å, in this example, 30 Å.

Also, in FIG. 1, the linear laser beam irradiated onto the substrate 105to be processed is 0.34 mm width×135 mm length. The energy density of alaser beam on a surface to be irradiated is set to a range of 100 to 500mJ/cm², for example, 260 mJ/cm². The linear laser beam is scanned bymoving the table 106 in one direction at 2.5 mm/s. The oscillationfrequency of the laser beam is set to 200 Hz, and when an attention ispaid to one point of an object to be irradiated, laser beams of 10 to 50shots are irradiated thereon.

In this way, laser-annealing is conducted on the crystalline siliconfilm 203, to thereby improve the crystallinity (FIG. 2B).

Most of the silicon oxide film 204 is scattered by the plural times ofirradiation of pulsed laser beams because it is extremely thin.

Thereafter, the substrate 105 to be processed is transferred to thecooling chamber 310, and after cooling, the substrate 105 is received inthe cassette 312 of the load/unload chamber 306.

Since the cooling process is conducted in the air atmosphere, the uppersurface of the crystalline silicon film 203 is liable to be oxidizedduring the cooling process. Also, in laser-annealing in an atmospherecontaining oxygen therein, even though the silicon oxide film 204 isscattered by the plural times of irradiation of laser beams, there is acase in which the upper surface of the silicon film which has beencrystallized is newly oxidized by oxygen contained in the atmosphere.Further, there is a case in which all of the silicon oxide film 204 isnot scattered even though it is subjected to laser irradiation. Asdescribed above, because the silicon oxide film is liable to remain onthe upper surface of the crystalline silicon film 203 after thecompletion of the laser annealing process, it is preferable that theupper surface of the crystalline silicon film 203 is reduced by the HFaqueous solution or the mixture solution of HF and H₂O₂ before shiftingto the subsequent process, to thereby remove the silicon oxide film.

Now, a comparison will be made between the crystalline silicon filmformed by the above process and the crystalline silicon film formed inanother atmosphere. As in the above-mentioned method, an atmosphereapplied for laser-annealing and the energy density of a laser beam arechanged to manufacture a crystalline silicon film. The atmosphere asapplied is N₂/H₂ (3%) and N₂ 100%. All of the respective gases are setto 99.99999% (7N) or higher in purity, and the atmosphere is set to theatmospheric pressure.

FIG. 4 shows a relation between the energy density of a laser beam andthe Raman half-value and half-width of the crystalline silicon filmwhich has been laser-annealed in the case where laser-annealing isconducted in a variety of atmospheres. The Raman half-value andhalf-width means ½ of the Raman half-value width. In FIG. 4, thecrystalline silicon film which has been manufactured in N₂/O₂ (20%)atmosphere which is used in the above process as an atmospherecontaining oxygen therein is indicated as ⋄, the crystalline siliconfilm which has been manufactured in N₂/H₂ (3%) atmosphere is indicatedby ∘, and the crystalline silicon film which has been manufactured in N₂100% atmosphere is indicated by.

It is understandable from FIG. 4 that the crystalline silicon film whichhas been laser-annealed in the atmosphere containing oxygen therein inaccordance with the present invention is more lowered in the Ramanhalf-value and half-width as the energy density is increased, that is,the crystallinity is improved.

Naturally, even though laser-annealing is conducted in an atmospherecontaining oxygen therein, if the energy density of the laser beam istoo increased, the entire film is largely roughened while thecrystallinity is improved. This makes it difficult to use the film as adevice such as a thin-film transistor. In this example, the energydensity of the laser beam is preferably set to 270 mJ/cm² or less.

On the other hand, in a range of the energy density shown in FIG. 4, thecrystallinity is low in any cases of other atmospheres.

The laser-annealing in the above atmosphere containing oxygen thereinmay be conducted not in the atmospheric pressure, but in a pressurelower than the atmospheric pressure, in particular, under the reducedpressure of 0.01 to 700 Torr. With the conduction of laser annealingunder the above reduced pressure, the roughness of the surface or theentirety of the annealed crystalline silicon film can be reduced.

Thereafter, a thin-film transistor (TFT) is fabricated using thecrystalline silicon film 203 thus fabricated. First, the crystallinesilicon film 203 is etched to form an island-like region 205.

Then, a silicon oxide film that forms a gate insulating film 206 isformed with a thickness of 1200 Å through the plasma CVD technique. TEOSand oxygen are used as raw gas. The temperature of the substrate whenforming a film is set to 250 to 380° C., for example, 300° C. (FIG. 2C).

Subsequently, a gate electrode is fabricated. An aluminum film 300 to8000 Å, for example, 6000 Å in thickness is deposited through thesputtering technique. Silicon of 0.1 to 2% may be contained in thealuminum film. The above film is etched to fabricate a gate electrode207.

Then, impurities are added to the silicon film 203. In the case offabricating an n-channel TFT, phosphorus ions are implanted into theisland region 205 through the ion doping technique with the gateelectrode as a mask. The doping gas as used is phosphine (PH₃). Theaccelerating voltage is set to 10 to 90 kV, for example, 80 kV, and thedose amount is set to 1×10¹⁴ to 5×10¹⁵ atoms/cm², for example, 1×10¹⁵atoms/cm². The temperature of the substrate is set to the roomtemperature. As a result, a channel formation region 210 is formed, anda source 208 and a drain 209 are formed as the n-type impurity regions.

Also, in the case of fabricating the p-channel type TFT, boron ions areimplanted into the island region 205 through the ion doping techniquewith the gate electrode as a mask. The doping gas as used is, forexample, diborane (B₂H₆) which has been diluted to 5%. The acceleratingvoltage is set to 60 to 90 kV, for example, 65 kV, and the dose amountis set to 2×10¹⁵ to 5×10¹⁵ atoms/cm², for example, 3×10¹⁵ atoms/cm². Thetemperature of the substrate is set to the room temperature. As aresult, a channel formation region 210 is formed, and a source 208 and adrain 209 are formed as the p-type impurity regions (FIG. 2D).

Subsequently, in order to activate the impurities doped, laser-annealingis conducted by the linear laser beam, again using the laser annealingunit shown in FIG. 3. The atmosphere within the laser irradiationchamber 101 is set to air (atmospheric pressure). The energy density ofa laser beam on a surface to be irradiated is set to a range of 100 to350 mJ/cm², for example, 160 mJ/cm². The linear laser beam is scanned.When an attention is paid to one point of an object to be irradiated,laser beams of 20 to 40 shots are irradiated thereon. The temperature ofthe substrate is set to 200° C. Thereafter, thermal annealing isconducted at 450° C. for 2 hours in a nitrogen atmosphere (FIG. 2E).

Subsequently, a silicon oxide film 6000 Å in thickness is formed throughthe plasma CVD technique to form an interlayer insulating film 211.Then, contact holes are defined in the interlayer insulating film 211 byetching. In addition, a multi-layer film made of metallic material, forexample, titanium and aluminum is formed and etched to form a sourceelectrode/wiring 212 and a drain electrode/wiring 213 through thecontact holes.

Finally, thermal annealing is conducted at 200 to 350° C. in a hydrogenatmosphere under one atmospheric pressure.

In the above manner, a plurality of n- or p-channel crystalline TFTs areformed. Those TFTs are excellent in movability such that the n-channelTFT is 70 to 120 cm²/Vs and the p-channel TFT is 60 to 90 cm²/Vs inmobility (FIG. 2F)

Second Embodiment

A second embodiment shows an example in which after a silicon oxide filmhas been formed on the upper surface of a non-monocrystal silicon filmin an oxygen atmosphere, laser-annealing is conducted on the film in anitrogen atmosphere. In the second embodiment, a laser annealing unitshown in FIG. 5 is employed. A cross-sectional view taken along a lineA–A′ of the laser irradiation chamber 101 in FIG. 5 corresponds to FIG.1.

As in the first embodiment, after a substrate 105 to be processed havinga substrate 201 shown in FIG. 2 on which an under film 202 and acrystalline silicon film 203 which has been crystallized by thermalannealing are formed is cleaned by an HF aqueous solution or a mixturesolution of HF and H₂O₂ so that a natural oxide film is removed from thefilm 203, it is received in a cassette 312, and the cassette 312 isdisposed in a load/unload chamber 306.

The substrate 105 to be processed which is transferred from theload/unload chamber 306 is transferred to a preliminary heating chamber501 after it has been subjected to alignment.

As shown in FIG. 5, the preliminary heating chamber 501 includes a vaporair-exhaust pump 502 for reducing a pressure in a space where asubstrate is mounted, and gas supply pipes 503, 504 which are capable ofsupplying oxygen or other gases to the space where the substrate ismounted.

After vacuum is produced in the space where the substrate is mounted bythe vacuum gas-exhaust pump 502 connected to the preliminary heatingchamber 501, oxygen is supplied from a gas supply pipe 503, and nitrogenis supplied from a gas supply pipe 504, respectively, so as to providean atmosphere of oxygen 5% and nitrogen 95% (both are 99.99999 (7N) inpurity) (atmospheric pressure) within the substrate holder. Then, whenpreliminary heating is conducted at 50 to 300° C., for example, 200° C.,the silicon oxide film 204 is simultaneously formed with 20 to 40 Å, forexample, 30 Å.

After vacuum is produced within the laser irradiation chamber 101 shownin FIG. 1 by the vacuum air-exhaust pump 108, nitrogen is supplied froma gas supply pipe 110, to provide an atmosphere of nitrogen 100%(99.99999 (7N) in purity). In this situation, pressure is set toatmospheric pressure.

The substrate to be processed on which the silicon oxide film 204 hasbeen formed in the preliminary heating chamber 501 is transferred to thelaser irradiation chamber 101 after it has been subjected to alignment.The substrate 105 to be processed which has been transferred has beenheated nearly to 200° C., and reaches a temperature proper forlaser-annealing, in this example, 200° C. by heating for a very shortperiod of time (several minutes) with the heater within the table 106 inthe state where it is mounted on the stage 111.

Thereafter, laser-annealing is conducted under the same conditions asthat in the first embodiment except for atmosphere. In this manner,laser-annealing is conducted on the crystalline silicon film 203 toimprove the crystallinity (FIG. 2B).

Most of the silicon oxide film 204 is scattered by the plural times ofirradiation of pulsed laser beams because it is extremely thin.

Thereafter, the substrate 105 to be processed is transferred to thecooling chamber 310, and after cooling, the substrate 105 is received inthe cassette 312 of the load/unload chamber 306.

It is preferable that the upper surface of the crystalline silicon film203 is reduced by the HF aqueous solution or the mixture solution of HFand H₂O₂ before shifting to the subsequent process, to thereby removethe silicon oxide film.

Thereafter, a thin-film transistor is formed in accordance with FIGS. 2Cto 2F as in the first embodiment.

In the case of the second embodiment, the substrate 105 to be processedis transferred within the laser irradiation chamber 101 where anatmosphere is identical with or different from that of the preliminaryheating chamber 501, to require no period of time for formation of thesilicon oxide film, or to reduce the processing time, thereby beingcapable of conducting laser annealing and reducing the manufactureprocess.

Also, in the second embodiment, the atmosphere within the laserirradiation chamber 101 is set to a nitrogen atmosphere. However, it maybe other atmospheres, for example, oxygen 20% and nitrogen 80% as in thefirst embodiment.

It should be noted that the laser-annealing in a nitrogen atmosphere hasthe effect of suppressing the occurrence of ridges (the roughness of thesurface of the crystalline silicon film after being laser-annealed) incomparison with other air, an atmosphere containing oxygen therein, anatmosphere containing hydrogen therein, etc.

Third Embodiment

A third embodiment shows an example in which laser annealing isconducted in the air (atmospheric pressure) particularly withoutcontrolling the atmosphere after the silicon oxide film 204 has beenformed on the upper surface of the crystalline silicon film 203 in thepreliminary heating chamber 501 shown in FIG. 5 as in the secondembodiment.

In the case of laser-annealing in the air, laser-annealing excellent incrystallinity, quality uniformity, the use efficiency of energy can beconducted because the silicon oxide film 204 is formed, in comparisonwith a case where laser annealing is merely conducted in the air withoutforming the silicon oxide film 204.

In particular, if the atmosphere may not be controlled, no laserirradiation chamber 101 which is an atmosphere controllable vessel maybe provided.

Fourth Embodiment

In the process of forming the crystalline silicon film 203 by thermalcrystallization in the first embodiment (FIG. 2A), the upper surface ofthe crystalline silicon film 203 is oxidized by the cooling process (airatmosphere) after thermal crystallization, to thereby form a siliconoxide film having about several 10 Å thickness.

In the first embodiment, the silicon oxide film is removed by cleaningbefore the laser annealing process. However, in the fourth embodiment,laser annealing is conducted on the film by the laser annealing unitshown in FIG. 3 as it is without removing the silicon oxide film.

As in the second embodiment, in the case where laser-annealing isconducted on the crystalline silicon film 203 in a nitrogen atmosphere,crystallinity, quality uniformity, the use efficiency of laser energycan be remarkably improved in comparison with a case where laserannealing is merely conducted in the nitrogen atmosphere without formingthe silicon oxide film.

Fifth Embodiment

A fifth embodiment shows an example of a continuous processing unit usedin a sixth embodiment. The continuous processing unit can implement aprocess of cleaning the non-monocrystal silicon film, and a laserannealing process or a heating (silicon oxide film forming) processcontinuously without being exposed to the air.

FIG. 6 shows an upper view of the continuous processing unit in thisembodiment. The unit shown in FIG. 6 has a structure where a substratecleaning chamber is added to the unit shown in FIG. 3.

In FIG. 6, a substrate transfer chamber 601 is connected with a laserirradiation chamber 602, a preliminary heating chamber 603, a coolingchamber 604 and a cleaning chamber 607 through gate valves 608 to 611.Also, the substrate transfer chamber 601 is connected with a load/unloadchamber 605 through an alignment chamber 606 and a gate valve 612.

Within the substrate transfer chamber 601 is disposed a robot arm 613 assubstrate transfer means that transfers a substrate 600. Within theload/unload chamber 605 is disposed a cassette 615 that receives aplurality of substrates therein.

In the structure shown in FIG. 6, a description relating to thesubstrate transfer chamber 601, the laser irradiation chamber 602, thepreliminary heating chamber 603, the cooling chamber 604, theload/unload chamber 605, and the alignment chamber 606 is omitted sincethey are identical in structure with the unit shown in FIG. 3 which hasbeen described in the first embodiment.

Also, the unit shown in FIG. 6 has air-tightness kept in each chamberand between the respective chambers. Each of those chambers is providedwith gas supply means and gas-exhaust means not shown so that theatmosphere and pressure in each chamber can be controlled arbitrarily.The substrate which is processed by the above unit is isolated from theexternal atmosphere, thereby being capable of preventing the substratefrom being in contact with the air.

In FIG. 6, the cleaning chamber 607 includes a stage 616, a cap 617 anda cleaning solution outflow nozzle 618. The stage 616 fixedly sucks therear surface of the substrate which has been transferred into thecleaning chamber 607 by vacuum, and then rotates the substratehorizontally. The cleaning solution outflow nozzle 618 discharges thecleaning solution to the center of the rotating surface of thesubstrate.

The preferred cleaning solution is an aqueous solution where HF 0.5 wt %and H₂O₂ 0.5 wt %, etc., are mixed. Instead, an aqueous solution of HFmay be used. The cleaning solution allows a natural oxide film,impurities, etc., to be removed from the upper surface of thenon-monocrystal silicon film.

The cap 617 is disposed so as to surround the periphery of the substratewhen rotating the substrate. When transferring the substrate, the cap617 is disposed at a position lower than a substrate fixing position onthe upper surface of the stage so as to prevent the obstruction oftransfer. The cap 617 receives the cleaning solution that scattersaround its circumference by the rotation of the substrate, and thenexhausts it downward.

A cleaning process by the unit shown in FIG. 6 will be described. Afterthe substrate 614 is transferred into the cleaning chamber and thenfixed onto the upper surface of the stage 616 by vapor-suction, thesubstrate rotates at a predetermined r.p.m. In this situation, thecleaning solution is discharged from the cleaning solution outflownozzle 618 to the center of the substrate rotating surface.

The discharged cleaning solution spreads from the center of thesubstrate outwardly concentrically circularly due to a centrifugalforce, and after the cleaning solution reaches the periphery of thesubstrate, it is scattered to the cap 617 and then exhausted.

After the above state is maintained for several 10 seconds to severalminutes, the outflow of the cleaning solution is stopped, and r.p.m. ofthe substrate is increased to dry the cleaning solution.

In the above manner, the cleaning process is completed. Thereafter, thesubstrate 604 is moved to another chamber such as the preliminaryheating chamber or the laser irradiation chamber by the transfer means613.

With the unit shown in FIG. 6, the substrate cleaning process, that is,the process of removing the natural oxide film, the impurities, dusts orthe like on the upper surface of the non-monocrystal silicon film, thelaser annealing process which is conducted on the non-monocrystalsilicon film in an oxygen atmosphere or the heating process (oxide filmforming process) in the oxygen atmosphere can be conducted continuouslywithout being exposed to the air.

As a result, the thin silicon oxide film formed on the upper surface ofthe non-monocrystal film is made high in quality without any impurities,thereby enabling excellent crystallization due to laser annealing.

Furthermore, with the unit shown in FIG. 6, cleaning the upper surfaceof the crystalline silicon film which has been subjected to thelaser-annealing process can be conducted continuously. As a result, thecrystalline silicon film having a clean surface can be provided for aprocess subsequent to the laser-annealing process for a shorter periodof time, thus contributing to a reduction in a required manufacturetime.

It should be noted that in this embodiment, the substrate cleaning is ofthe system in which the substrate is rotated using the cleaningsolution. This system can prevent blooming or contamination of the glasssubstrate due to the cleaning solution because there is very littlepossibility of sticking the cleaning solution on the rear surface sideof the substrate. Further, because the cleaning solution can be dried byonly the rotation of the substrate, the entire cleaning process can beshortened in time. Also, because an equipment is compact and simple, theuse of the equipment for the multi-chamber type continuous processingunit shown in FIG. 6 is effective because the location area of thedevice is reduced, and the design is facilitated.

However, the substrate cleaning system of this embodiment is not limitedto this. For example, it may be of a structure in which the cleaningsolution is discharged on the upper surface of the substrate withoutrotating the substrate.

Also, the non-monocrystal silicon film may be exposed to the reducinggas atmosphere.

Sixth Embodiment

A sixth embodiment shows an example in which a substrate cleaningprocess and a laser-annealing are continuously conducted without beingexposed to the air, using a unit shown in FIG. 6.

A process of manufacturing a thin-film transistor in accordance with thesixth embodiment will be described with reference to FIG. 2. First, asin the first embodiment, a silicon oxide film 202 which is 2000 Å inthickness is formed as an under layer on a substrate 201 which is madeof Corning 1737 having 127 mm² in area, and a amorphous silicon filmwhich is 500 Å in thickness is formed on the silicon oxide film 202,which process is continuously conducted through the plasma CVDtechnique.

Subsequently, after a nickel acetate aqueous solution as in the firstembodiment is coated on the amorphous silicon film, thermal annealing isconducted on the film at 600° C. for 4 hours, to thereby form acrystalline silicon film 203 (FIG. 2A).

Then, the cleaning of the crystalline silicon film and the laserannealing process in the oxygen atmosphere are continuously conducted bythe continuous processing unit shown in FIG. 6.

Each chamber of the continuous processing unit shown in FIG. 6 isisolated from the air, and the atmosphere is made up of a clean gaswhich is cleaned so that impurities, etc., are removed therefrom. Forexample, it is preferable to use an inactive gas such as nitrogen, argonor helium, or oxygen mixed with each of those inactive gases, and so on.Also, the cleaned air may be used instead.

First, a substrate to be processed on which a crystalline silicon film203 is formed is received in a cassette 615, and the cassette 615 isdisposed in a load/unload chamber 606.

The substrate to be processed which is transferred from the load/unloadchamber 606, after being subjected to alignment in an alignment chamber605, is transferred to the cleaning chamber 607 where the natural oxidefilm and impurities are removed from the upper surface of thecrystalline silicon film 203.

In the cleaning chamber 607, the substrate 614 is fixed to the stage616, and cleaning is conducted on the substrate 614 using a cleaningsolution while rotating.

The cleaning solution is discharged from a nozzle 618 to the center ofthe substrate rotating surface. The discharged cleaning solution movesfrom the center of the substrate outwardly concentrically circularly dueto a centrifugal force of the substrate rotation. Thereafter, thecleaning solution scatters around the periphery of the substrate, andthen exhausted after hitting on the cap 617. The cleaning solution inthis example is an aqueous solution where HF 0.5 wt % and H₂O₂ 0.5 wt %,etc., are mixed. Instead, an aqueous solution of HF may be used.

The substrate is rotated at 100 to 1000 rpm, for example, 300 rpm for 10seconds to 5 minutes, in this example, 1 minute, while receiving thecleaning solution. Thereafter, the outflow of the cleaning solution isstopped, and the substrate is rotated for about 30 seconds with anincrease in rpm of the substrate for drying the upper surface of thesubstrate. The rpm of the substrate during drying is set to 2500 to 4000rpm, in this example, 3000 rpm.

Thereafter, the rotation of the substrate is stopped, and the substrateis transferred from the cleaning chamber 607 by the substrate transfermeans 613.

In the above manner, the upper surface of the crystalline silicon film203 on the substrate is cleaned so that the natural oxide film andimpurities are removed.

Subsequently, laser-annealing is conducted on the crystalline siliconfilm 203. The substrate exhausted from the cleaning chamber 607 istransferred to the laser irradiation chamber 602 directly or after beingheated in the preliminary heating chamber 603.

As a result, the crystalline silicon film which has been cleaned istransferred to the laser irradiation chamber 602 continuous to thecleaning chamber 607 without being in contact with the air.

After heating up to a predetermined temperature using the preliminaryheating chamber 603, the substrate is transferred to the laserirradiation chamber, thereby being capable of reducing a substrateheating time within the laser irradiation chamber.

Then, laser annealing is conducted in the oxygen atmosphere. The laserirradiation chamber 602 is in an atmosphere of oxygen 20% and nitrogen80%. Then, laser annealing is conducted on the crystalline silicon film203 in the oxygen atmosphere under the same conditions as those in thefirst embodiment, thereby improving the crystallinity (FIG. 2B).

In this embodiment, because the continuous processing unit shown in FIG.6 is used, the substrate to be processed is not in contact with the airfrom the preceding cleaning process to the laser annealing process atall, but in contact with only the clean atmosphere without anyimpurities. For that reason, the natural oxide film formed in the airand the impurities in the air are considerably removed in the thinsilicon oxide film 204 formed on the upper surface of the crystallinesilicon film 203 and in the vicinity thereof during the laser-annealingprocess. As a result, the silicon oxide film 204 is formed into a verypure silicon oxide film. Thus, laser-annealing can be more effectivelyconducted in comparison with the first embodiment.

In other words, the thickness and the quality of the silicon oxide film204 to be formed become more uniform on the upper surface of thecrystalline silicon film 203 in comparison with the first embodiment,with the result that the uniformity of the film crystallized bylaser-annealing on the substrate surface is improved.

Furthermore, the invasion by impurities into the crystalline siliconfilm 203 during laser-annealing is more reduced. As a result, a varietyof characteristics such as the mobility or the threshold value of thethin-film transistor manufactured can be more stabilized in thesubstrate surface as well as between the respective lots.

After the completion of the laser-annealing process, the substrate istransferred to the cooling chamber 604 and gradually cooled as occasiondemands.

Thereafter, although the substrate may be transferred to the load/unloadchamber, the silicon oxide film is liable to remain on the upper surfaceof the crystalline silicon film 203 after the completion of the laserannealing process.

In other words, in laser-annealing in an atmosphere containing oxygentherein, even though the silicon oxide film 204 is scattered by theplural times of irradiation of laser beams, there is a case in which theupper surface of the silicon film which has been crystallized is newlyoxidized by oxygen contained in the atmosphere. Further, there is a casein which not all of the silicon oxide film 204 is scattered even thoughit is subjected to laser irradiation.

Accordingly, it is largely effective that the substrate is againtransferred to the cleaning chamber and then cleaned after thecompletion of the laser annealing process.

As a process, after the substrate has been discharged from the laserirradiation chamber 602 or the annealing chamber 604, it is taken in thecleaning chamber 607 where the upper surface of the crystalline siliconfilm 203 is cleaned so as to remove the silicon oxide film, theimpurities, etc. The conditions are made identical with those in thecleaning process before the laser-annealing process.

In this manner, the laser annealing process and the cleaning process, orthe annealing process and the cleaning process are conductedcontinuously without being exposed to the air, thereby being capable ofobtaining high cleaning property on the upper surface of the crystallinesilicon film for a short period of time.

Thereafter, the substrate for which the cleaning process has beencompleted is transferred from the cleaning chamber 607 to theload/unload chamber 606 by the substrate transfer means 613, and thenreceived in the cassette 615.

Then, through the processes identical with those in the firstembodiment, a thin-film transistor is completed (FIG. 2C to 2F).

The thin-film transistor thus fabricated is improved in a variety ofcharacteristics and has stabilized characteristics in the substratesurface and between the respective lots.

Seventh Embodiment

A seventh embodiment shows an example in which, after the silicon oxidefilm has been formed on the upper surface of the non-monocrystal siliconfilm in the oxygen atmosphere using the continuous processing unit shownin FIG. 6, it is laser-annealed in the nitrogen atmosphere.

As in the sixth embodiment, a thin-film transistor is fabricated inaccordance with FIG. 2. A silicon oxide film 202 as an under film and anamorphous silicon film are continuously formed on the substrate 201.After a nickel acetate aqueous solution is coated on the amorphoussilicon film, thermal annealing is conducted on the film at 600° C. for4 hours, to thereby form a crystalline silicon film 203 (FIG. 2A).

Then, the upper surface of the crystalline silicon film 203 is cleanedin the cleaning chamber 607 as in the sixth embodiment. As a result, thenatural oxide film and the impurities are removed from the upper surfaceof the crystalline silicon film 203.

Subsequently, the substrate is transferred to the preliminary heatingchamber 603. The preliminary heating chamber 603 is in the atmosphere ofoxygen 5% and nitrogen 95% (both are 99.99999 (7N) in purity)(atmospheric pressure). Then, when preliminary heating is conducted at50 to 300° C., for example, 200° C., the thin silicon oxide film 204 issimultaneously formed with 20 to 40 Å, for example, 30 Å on the uppersurface of the crystalline silicon film 203.

The silicon oxide film 204 thus formed becomes a very pure film mixedwith few impurities because the upper surface of the crystalline siliconfilm 203 is cleaned by the preceding cleaning process and also is notexposed to the air.

After the completion of the preliminary heating, the substrate to beprocessed is moved into the laser irradiation chamber 602 from thepreliminary heating chamber 603 without being exposed to the air. Inthis example, the laser irradiation chamber 602 is in a nitrogenatmosphere.

Then, laser-annealing is conducted under the conditions identical withthose in the sixth embodiment except for atmosphere, to thereby improvethe crystallinity of the crystalline silicon film 203 (FIG. 2B).

The crystalline silicon film 203 which has been laser-annealed isimproved in the uniformity of crystallization caused by laser annealingin the substrate surface in comparison with that obtained in the secondembodiment. Further, a variety of characteristics such as the mobilityor the threshold value of the thin-film transistor fabricated are morestabilized in the substrate surface as well as between the respectivelots.

Moreover, since the atmosphere when conducting laser-annealing is set toa nitrogen atmosphere, the occurrence of ridges is suppressed incomparison with an oxygen atmosphere. As a result, in addition to animprovement in the crystallinity and the quality of the crystallinesilicon film obtained by conducting the cleaning process and the laserannealing process continuously with the substrate being not exposed tothe air, the ridges are suppressed, thereby being capable of making thequality of the crystalline silicon film more excellent.

Thereafter, as in the sixth embodiment, a thin-film transistor is formedin accordance with FIGS. 2C to 2F.

In the process of this embodiment, no period of time for forming thesilicon oxide film 204 within the laser irradiation chamber is requiredas in the second embodiment. Hence, the manufacture process time can bereduced.

This embodiment can be implemented if a clean atmosphere is providedeven though the atmosphere when conducting laser annealing is not anitrogen atmosphere.

As described above, according to the present invention, thecrystallinity and the uniformity can be remarkably improved, and theuseful efficiency of energy can be also remarkably improved incomparison with a case where laser-annealing is conducted in the air orother atmospheres.

The foregoing description of a preferred embodiment of the invention hasbeen presented for purposes of illustration and description. It is notintended to be exhaustive or to limit the invention to the precise formdisclosed, and modifications and variations are possible in light of theabove teachings or may be acquired from practice of the invention. Theembodiment was chosen and described in order to explain the principlesof the invention and its practical application to enable one skilled inthe art to utilize the invention in various embodiments and with variousmodifications as are suited to the particular use contemplated. It isintended that the scope of the invention be defined by the claimsappended hereto, and their equivalents.

1. A method for manufacturing a semiconductor device comprising thesteps of: forming a semiconductor film over a substrate; cleaning asurface of the semiconductor film by using a first solution; applying alaser beam to the cleaned surface of said semiconductor film to increasecrystallinity of the semiconductor film; removing an oxide film formedon a surface of the semiconductor film when applying the laser beam byusing a second solution after applying the laser beam; patterning thesemiconductor film after removing the oxide film; and forming a gateinsulating film on a surface of the patterned semiconductor film.
 2. Amethod according to claim 1, wherein said first solution comprises a HFaqueous solution or an aqueous solution containing HF and H₂O₂.
 3. Amethod according to claim 1, wherein said laser beam has an energydensity of 100 to 500 mJ/cm².
 4. A method for manufacturing asemiconductor device comprising the steps of: forming a semiconductorfilm over a substrate; cleaning a surface of said semiconductor film byusing a first solution; applying a laser beam to said semiconductor filmto increase crystallinity of the semiconductor film in the air; removingan oxide film formed on a surface of the semiconductor film whenapplying the laser beam by using a second solution after applying thelaser beam; patterning the semiconductor film after removing the oxidefilm; and forming a gate insulating film on a surface of the patternedsemiconductor film.
 5. A method according to claim 4, wherein said laserbeam is a linear laser beam.
 6. A method according to claim 4, whereinsaid laser beam has an energy density of 100 to 500 mJ/cm².
 7. A methodfor manufacturing a semiconductor device comprising the steps of:forming a semiconductor film over a substrate; cleaning a surface ofsaid semiconductor film by using HF aqueous solution or an aqueoussolution containing HF and H₂O₂; applying a laser beam to saidsemiconductor film to increase crystallinity of the semiconductor filmin the air; removing an oxide film formed on a surface of thesemiconductor film when applying the laser beam by using a secondsolution after applying the laser beam; patterning the semiconductorfilm after removing the oxide film; and forming a gate insulating filmon a surface of the patterned semiconductor film.
 8. A method accordingto claim 7, wherein said laser beam is a linear laser beam.
 9. A methodaccording to claim 7, wherein said laser beam has an energy density of100 to 500 mJ/cm².
 10. A method according to claim 1, wherein applyingthe laser beam comprises doing so in a nitrogen atmosphere.
 11. A methodaccording to claim 1, wherein the first and second solutions are thesame.
 12. A method according to claim 1, wherein the first and secondsolutions are different.
 13. A method according to claim 4, wherein thefirst and second solutions are the same.
 14. A method according to claim4, wherein the first and second solutions are different.
 15. A methodaccording to claim 7, wherein the first and second solutions are thesame.
 16. A method according to claim 7, wherein the first and secondsolutions are different.